N-phenylsuccinimide derivatives

ABSTRACT

WHEREIN R1 and R2 represent individually a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, a benzyl group or a phenyl group, which may have been substituted by a chlorine atom; R3 represents a hydrogen atom, a halogen atom or a methyl group; and X represents individually a halogen atom, provided that in case all of R1, R2 and R3 are hydrogen atoms at the same time, X represents other halogen atoms than chlorine atoms. Examples of said derivatives are N-(3&#39;&#39;,5&#39;&#39;-dihalogenophenyl)-3-methylsuccinimide, N-(3&#39;&#39;,5&#39;&#39;-dihalogenophenyl)-3,3-dimethylsuccinimide, N-(3,4,5-trihalogenophenyl)succinimide, N-(3,5-dihalogeno-4-methylphenyl)succinimide, N-(3,5-dibromophenyl)succinimide, N-(3&#39;&#39;,5&#39;&#39;-dihalogenophenyl)-3-phenylsuccinimide, N-(3&#39;&#39;,5&#39;&#39;-dihalogenophenyl)-3-(halogenophenyl)succinimide, N-(3&#39;&#39;,5&#39;&#39;-dihalogenophenyl)-3-benzylsuccinimide, and N-(3&#39;&#39;,5&#39;&#39;-dihalogenophenyl)-3-methyl-3-phenylsuccinimide. These compounds are prepared by cyclizing corresponding succinic acid monoanilides under dehydration conditions.   Novel N-phenylsuccinimide derivatives preferable as microbicides which are represented by the formula

United States Patent 1191 Fujinami et al.

[ June 26, 1973 N-PHENYLSUCCINIMIDE DERIVATIVES [75] Inventors: Akira Fujinami, Ashiya-shi; Toshiaki A Ozaki, Toyonaka-shi; Katsuji Nodera, Nishinomiya-shi; Keiichiro Akiba, Takarazuka-shi; Sigeo Yamamoto, Toyonaka-shi; Katsutoshi Tanaka, Takarazuka-shi; Tadashi Ooishi, Minoo-shi, all of Japan [73] Assignee: Sumitomo Chemical Company, Ltd.,

Higashi-ku, Osaka, Japan I 22 Filed: Aug. 1,1969

21 Appl. No.: 846,931

[30] Foreign Application Priority Data Aug. 12, 1968 Japan 43/57498 [.52] US. Cl. 260/3265 FM,.424/274 [51] Int. Cl C0 7d 27/10 [58] Field of Search 260/3265 FM [56] References Cited I UNITED STATES PATENTS 3,586,697 6/1971 Ozaki et al 260/3265 3,162,648 12/1964 Miller 260/5265 OTHER PUBLICATIONS Allen et al. Chem. Abs., 46:3701 (1952). Chem. Abs., 6029157 (1964), abs. of Belg. Pat. No.

Primary Examiner-Joseph A. Narcavage Attorney-Stevens, Davis, Miller & Mosher 57 ABSTRACT I Novel N-phenylsuccinimide derivatives preferable as microbicides which are represented by the formula wherein R and R represent individually a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, a benzyl group or a phenyl group, which may have been substituted by a chlorine atom; R represents a hydrogen atom, a halogen atom or a methyl group; and X represents individually a halogen atom, provided that in case all of R R and R are hydrogen atoms at the same time, X represents other halogen atoms than chlorine atoms. Examples of said derivatives are A N-( 3 ,5 -dihalogenophenyl )-3 -methylsuccinimide N-( 3 ',5 -dihalogenophenyl)-3 ,3-dimethylsuccinimide, N-( 3 ,4 ,S-trihalogenopheny] )succinimide N-(3,5-dihalogeno-4-methylphenyl)succinimide, N-(3,5-dibromophenyl)succinimide, N-( 3 ,5 '-dihalogenophenyl)-3-phenylsuccinimide, N-( 3 ,5 '-dihalogenophenyl )-3-(halog'enophenyl )succinimide, N-(3',5-dihalogenophenyl)-3-benzylcussinimide,

and N-( 3 ,5 '-dihalogenophenyl )-3-methyl-3- phenylsuccinimide. These compounds are prepared by cyclizing corresponding succinic acid monoanilides under dehydration conditions.

5 Claims, No Drawings 1 N-PHENYLSUCCINIMIDE DERIVATIVES This invention relates to novel N-phenylsuccinimide derivatives valuable as microbicides.

More particularly, the invention pertains to N- phenylsuccinimide derivatives represented by the formula wherein R and R represent individually a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, a benzyl group, a phenyl group or a chlorine atom substituted phenyl group; R represents a hydrogen atom, a halogen atom or a methyl group; and X represents a halogen atom, provided that in case R R and R are hydrogen atoms at the same time, X represents other halogen atom than a chlorine atom.

Heretofore, not a few N-phenylsuccinimide derivatives have been well known. However, all the N- phenylsuccinimide derivatives provided in accordance with the present invention are novel compounds and have specifically high microbicidal activities, which can by no means be expected from other known homologues. It wasfound that the specific microbicidal activities of the present compounds are derived from the fact that halogen atoms have been substituted in the 3- and 5-positions of the benzene rings forming the skeletons of the present compounds The present invention has been completed on the basis of theabovementioned new finding.

OBJECT It is therefore the object of the present invention to provide novel N-phenylsuccinimide derivatives, a process for the preparation thereof, and microbicidal composition containing said derivatives as active ingredients.

CHEMICAL COMPOUNDS Among the N-phenylsuccinimide derivatives of the present invention, typical compounds having prominent fungicidal activities are enumerated below. Compound No.

,7 oH3-oH-d Hz=C N-(3',5'-Dichlorophenyl) 3-methylsuccinimide W Chad-.. A H h a g Cl CH3-C l )G CHr-C N-(3',5-Dichlorophenyl)-3,3-dimethylsuccinimide N43,4,s rrich1ompheay1 ucamm'iae ll 01 CHr-C N CH; CHFE l N-( 3 ,5-Dichloro-4'-methylphenyl )succini'mide N-( 3,5 '-Dichlorophenyl)-3-phenylsuccinimide N-( 3,5 '-Dichlorophenyl)-3-( 2 -chlorophenyl succinimide N-( 3 ',5 '-Dibromophenyl)-3-phenylsuccinimide om m ll I CH2C N-( 3',5 '-Dich1orophenyl)-3-benzylsuccinimide N-( 3',5'-Dichlotophenyl)-3-methyl-3-phenylsuccinimide N-( 3,5-Dibromophenyl)succinimide H Cl CHzC\ /N -Cl CH3CC A 1 CH3 N-( 3 ,4',5 -Trichlorophenyl)-3 ,3-dimethylsuccinimide UTILITY The compounds of the present invention have prominent effects on rice blast fungus (Pyricularia oryzae), rice sheath blight fungus (Pellicularia sasakii), rice Helminthosporium leaf spot fungus (Cochliobolus miyabeanus), and stem rot of kidney bean fungus (sclerotinia sclerotiorum), powdery mildew fungus (Spaerotheca fuliginea), etc. which attack agricultural and horticultural crops and hence are utilizable as plant diseasecontrolling agents. Further, they are effectively usable also for the control of Aspergillus niger which propagates in industrial products and causes serious damage. Nevertheless, they scarcely have detrimental actions on animals and plants. Fungicides having such broad antimicrobial spectra and microbicidal effects have never been seen heretofore. Accordingly, the utility of the present compounds in the industrial fields is tremendous.

PROCESS The compounds of the present invention are prepared by subjecting to dehydration reaction to cyclize succinic acid monoanilide derivatives represented by the formula,

wherein R R R and X are as defined previously.

STARTlNG COMPOUNDS 3 )-methylsuccinic acid monoamide. I

'ethylene-bis-dithiocarbamate N-(3,5'-Dichlorophenyl)-2,2(or

cinic acid monoamide.

N-(3,4,5-Trichlorophenyl)-succinic acid monoamide.

N-( 3 ,5 '-Dichloro-4-methylphenyl)-succinic monoamide.

N-(3',5-Dichlorophenyl)-2(or acid monoamide.

phenyl)-succinic acid monoamide.

N-(3,5'-Dibromophenyl)-2(or 3)-phenylsuccinic acid monoamide.

acid monoamide.

N-(3',5-Dichlorophenyl)-2-methyl-2- phenylsuccinic acid monoamide.

N-(37,5-Dichlorophenyl)-3-methyl-3- phenylsuccinic acid monoamide.

N-(3,5-Dibromophenyl)-succinic acid monoamide N-(3,4',5'-Trichlorophenyl)-2,2(or 3,3)-dimethylsuccinic acid monoamide.

In the present process, the reaction may be effected by merely fusing the starting monoanilide derivative at an elevated temperature to obtain the desired product. The fusion temperature is adequately about 170C. Desirably, the starting monoanilide derivative is heated under stirring at about C. in the presence of a suitable dehydrating agent, e.g. acetic anhydride, acetyl chloride, phosphorus pentachloride, phosphorus oxychloride or the like, preferably acetic anhydride, wher eby the desired product is easily obtained in a high yield. In this case, the reaction time is adequately about 1 hour.

3,3 )-dimethylsucacid 3 )-phenylsuccinic 3 )-(2"-chloro- 3 )-benzylsuccinic FUNGICIDAL COMPOSITlONS dichlorophenylmaleic acid imide, 3,5-dichlorophenylsuccinic acid imide, 3,5-dichlorophenylitaconic acid imide, 0,0-diethyl-S-benzyl phosphorothioate, O- ethyl-SS,-diphenyl phosphorodithiolate, O-butyl-S- benzyl-S-ethyl phosphorodithiolate, 0,0.-dimethyl-O- (3-methyl 4-nitrophenyl) phosphorothioate, S-[ l,2-bis (ethoxycarbonyl) ethyl]0,0-dimethyl. phosphorodithioate, 0,0-dimethyl-S-(N-methyl carbamoylmethyl) phosphorodithioate, 0,0-diethyl-O-( 2-isopropyl-6- methyl-4-pyrimidinyl) 'thiophosphate, 3,4-dimethylphenyl N-methyl carbamate,

p ected depending on combinations. Furthermore, they I zinc- N-trichloromethylthio- EXAMPLES l-ll Preparation Process All these examples. were effected according to the following standard operational process:

A mixture comprising 0.] mole of a succinic acid monoanilide derivative of the formula (ll) or (III), 50 g. of acetic anhydride and l.0 g."of anhydrous sodium acetate is fed to a 100 cc. four-necked flask and is stirred at 90 100C. for 1 hour. Thereafter, acetic acid and acetic anhydride are removed by reduced pressure distillation, and the residue is water-washedand dried, whereby a desired product is obtained in a substantially pure form and in a high yield. When recrystallized from alcohol, the product can be brought into a pure form.

Results obtained by practicing the above-mentioned standard operational process are shown in Table l.

Preparation of microbicidal compositions:

The active compounds employed in the examples shown below are represented by the aforesaid compound numbers.

EXAMPLE l2 DUST Three parts of the compound (3) and 97 parts of clay were thoroughly pulverized and mixed together to obtain a dust containing 3 percent of active ingredient. In application, the dust was dusted as it was.

EXAMPLE l3 DUST Four parts of the compound (7) and 96 parts of talc were thoroughly pulverized and mixed together to obtain a dust containing 4 percent of active ingredient. In application, the dust was dusted as it was.

EXAMPLE l4 WETTABLE POWDER Fifty parts of the compound (4), 5 parts of a wetting agent of alkylbenzenesulfonate type and 45 parts of diatomaceous earth were thoroughly pulverized and mixed together to obtain a wettable powder containing 50 percent of active ingredient. In application, the wettable powder was dilutedwith water and was sprayed.

EXAMPLE .15 EMULSIFIABLE CONCENTRATE Ten parts of the compound (8), 60 parts of dimethylformamide, 20 parts of dioxane and parts of an emulsifier of polyoxyethylene phenylphenol polymer type were mixed together to obtain an emulsifiable concentrate containing 10 percent of active ingredient. In application, the emulsifiable concentrate was diluted with water and was sprayed.

EXAMPLE l6 GRANULES Five parts of the compound (9), 93.5 parts of clay and 1.5 parts ofa binder of polyvinyl alcohol type were thoroughly pulverized and mixed together. After kneading with water, the mixture was granulated and dried to obtain a granules preparation containing 5 percent of active ingredient. In application, the granule was sprinkled as it was.

EXAMPLE l7 COMPOSITE DUST Two parts of the compound (2), 1.5 parts of pentachlorobenzaldoxime, 1.5 parts of O-n-butyl-S-ethyl-S- benzyl phosphorodithiolate and 95 parts of clay were thoroughly pulverized and mixed together to obtain a dust containing 5 percent of active ingredients. In application, the dust was dusted as it was.

EXAMPLE l8 COMPOSITE DUST EFFECTS In order to substantiate excellent microbicidal effects of the present' compounds, typical test results will be shown in test examples set forth below.

2 TEST EXAMPLE 1 Effect of controlling rice blast (Pyricularia oryzae):

Rice plants (variety: Waseasahi"), which had been cultivated to the 3 leaves stage in flower pots of 9 cm. in diameter, were individually dusted by means of a bell jar duster with mg/pot of each of test chemicals in the form of dusts. After one day, the rice plants were sprayed and inoculated with a spore suspension of rice blast fungus (Pyricularia oryzae). 5 Days thereafter, the number of diseased spotsgenerated was counted to investigate the fungicidal effect of each test chemical, whereby the results shown in Table 2 were obtained. As seen in Table 2, the present compounds showed markedly excellent effects as compared with the control known compounds.

hats";

Actlve ingredient concen- Number of tration spots per Compound (percent) 10 leaves fi-CH-CHzCEECHz' 0 (Known compound) TI) 3. 0 213 /CCH:

fil- H-C Ha 0 (Known compound) (6 3. 0 167 C C H; 01- N\ (Known compound) Non-treatment 289 Control.

TEST EXAMPLE 2 Effect of controlling rice Helminthosporium leaf spot Cochliobolus miabeanus):

Rice plants (variety: Waseasahi"), which had been cultivated to the 4 leaves stage in flower pots of 9 cm. in diameter, were individually sprayed with l0 ml./pot of an aqueous dilute solution of each of test chemicals in the form of wettable powders. After one day, the rice plants were sprayed and inoculated with a spore sus-' pension of rice leaf spot fungus (Cochliobolus miyabeanus). Three days thereafter, the numberof diseased spots generated was counted to investigate-the fungicidal effect of each chemical, whereby the results shown in Table 3 were obtained. As seen in Table 3, the present compounds showed markedly excellent effects as compared with the control known compounds.

TABLE 3 TABLE 4 ominnctl Active in Active gradient ingredient.

coneen- Number eonoon- Degree tration of spots tration Compound (p.p.m.) per leaf 5 Compound (p.p.m.) damage 100 o 17.4 100 0 200 18.8 100 4 200 19.3 100 200 6.2 100 8 200 11.7 100 2 v 100 a 200 78.5 100 c 100 84 -NH S OzOHzCl I Cl (Known compound) Cl 200 71.7

Q-NHC 0 0 02m 100 103 c1 (Known compound) C-CHz Cl N\ (Known com oun p CCHCH:CH=CH2=* Non-treatment 98 g *Control.

(Known compound) TEST EXAMPLE 3 (H) 200 100 Effect of controlling rice sheath blight (Pellicularia /CCH;' sasakii Cl-Q-N I Rice plants (variety: Kinmaze) were cultivated in porcelain Wagner pots. When the plants had grown to l a height of 50 60 cm., a disk inoculum of the mycelium of rice sheath blight fungus (Pellicularia sasakii) Klowmmpmd) was inoculated on the leaf sheaths of individual stems 100 of the plants. After one day, the plants were sprayed with 10 mL/pot of an aqueous dilute solution of each l of test'chemicals in the form of emulsifiable concenl trates. Seven days thereafter, the size of each diseased 40 spot generated on the leaf sheath was measured to in- O vestigate the fungicidal effect of eath test chemical, (Known compound) whereby the results shown in Table 4 were obtained. As 0 200 100 seen in Table 4, the present compounds showed mark- L edly excellent controlling effects as compared with the I control known compounds. 01- T l The degree of damage set forth in the table was calculated in the following manner: 0

v (Known compound) Disease 0 No spot was observed on the leaf 5 (trade namey 15, 5 index sheaths. Non-treatment 100 1 Shades similar to spots were observed on the leaf sheaths. 2 Spots of less than 3 in size Tuz: An 80% \vettable powder containing: Percent g g observid on [he leaf.sheaths' Monomothylarsino-bis-dimethyl dithiocarbamnte Pots 0 more 3 m Zinc (limethyl dithioearbamate 40 were observed on the leaf sheaths. 40

2; (disease index X number of stems) Tetrnmethylthiuram disulfide TEST EXAMPLE 4 Effect of controlling powdery mildew (Sphaerotheca fuliginea) of cucurbitaceous plants:

Pumpkin plants (variety: Heian Kogiku") were cul-' tivated in flower pots of 12 cm in diameter. When the plants had grown to the 3-4 leaves stage, they were individually sprayed with 7 mL/pot of each of given concentration solutions of test chemicals in the form of wettable powders. One day after, the plants were sprayed and inoculated with a spore suspension of cucurbitaceous plant powdery mildew fungus (Sphaerotheca fuliginea). Ten days thereafter, the state of disease of four leaves at the upper portion of each plant was observed and the disease degree of the plant was calculated from the area of spots generated.

In each treatment, seven pots were tested to obtain the results shown in Table 5. As seen in Table 5, the present compounds showed marked excellent controlling effects as compared with the control known compounds.

TABLE 5 Active ingredient concen- Degree tration of Compound (p.p.m.) damage 500 as. o

(u) 500 42. 7 C-(H1I[ o l- N\ (Known compound) Non-treatment 55. it

*Controlu TEST EXAMPLE TABLE 6 Effective concentration (p.p.m.) Compound 3CH /iJ-CH1 x I l & C-CH-CH: l C-CH;

l I OH:

(Present compound) (Known) (Control) Test organisms Pyricularia oryzae 40 290 Cochliobolus 40 200 miyabeanus Alternaria kikuchiana 40 Z00 Pellicularia sasakii 200 200 Pythium aphanidermatum 200 200 Pellicularia 40 200 filamentosa Corticium rolfsii 200 200 Botrytis cinerea 8 200 Sclerotinia 8 200 sclerotiorum Alternaria mali 40 200 Glomerella cingulata 40 200 Xanthomonas oryzae 40 200 Note: 200 shows that no effect was observed at a concentrationof 200 p.p.m.

According to the same method, the growth-inhibiting effects of compounds on Aspergillus niger propagating in industrial products were investigated to obtain the results set forth in Table 7.

TABLE 7 Effective concentration (p,p.m.)

C-C H2 C Compound N N C-CI'ICHJ I 0 (Present compound) CH3 ll H: ll

(Known) (Control) Test organism:

Aspergillus m'gcr. 40

N 0TE.1,000 shows that no effect was observed at a concentration of 1,000 p.p.m.

What is claimed is:

1. An N-phenylsuccinimide derivative represented by the formula,

cu e 

2. N-(3'',5''-Dichlorophenyl)-3-methylsuccinimide
 3. N-(3'',5''-Dichlorophenyl)-3,3-dimethylsuccinimide
 4. N-(3,5-Dibromophenyl)succinimide
 5. N-(3,4,5-Trichlorophenyl)succinimide 